Polyurethanes chain extended with N,N bis(1,1-dioxohydrothienyl) diaminoalkanes

ABSTRACT

Certain N,N&#39;&#39;-bis(1,1-dioxohydrothienyl)diaminoalkanes, e.g., N, N&#39;&#39;-bis(1,1-dioxotetrahydro-3-thienyl)1,2-diaminopropane, useful as chain extenders for polyurethanes, especially high resiliency, flexible polyurethane foams.

' United States Patent Mao et al. Oct. 28, 1975 POLYURETHANES CHAINEXTENDED [56] References Cited WITH UNITED STATES PATENTSBIS(II'DIOXOHYDROTHIENYL) 3,383,365 5/l968 Tate et al 260/75 NHDIAMINOALKANES 3.655597 4/1972 StrflSSel 260/25 AZ Inventors: Chung-LingMao, Sandy Hook,

Conn.; Lynn A. Bakker, Granger,

lnd.

Assignee: Uniroyal, Inc., New York, NY.

Filed: Feb. 4, 1974 Appl. No.: 439,192

Primary ExaminerH. S. Cockeram Attorney, Agent, or Firm-James J. Long[57] ABSTRACT Certain N,N-bis( l ,l -dioxohydrothienyl)diaminoalkanes, e.g., N .N-bis( 1.1-diox0tetrahydro-3- thienyD-l .Z-dianinopropane.useful as chain extenders for polyurethanes, especially high resiliency,flexible polyurethane foams.

25 Claims, No Drawings POLYURETHANES CHAIN EXTENDED WITH N,N BIS( l l-DIOXOHYDROTHIENYL) DIAMINOALKANES This invention relates to certain'newN;N'-bis -('1, ldioxohydrothienyl) diaminoalkanes, a method ofchain-extending polyurethanes therewith,' and the resultingchain-extended polyurethanes.

In the manufacture of polyurethanes (long chain polyol'polyisocyanatereaction products) it is conventional to employ a chain extender whichis ordinarily a polyfunctional organic compound having two or morereactive hydrogen atoms (reactive toward isocyanate; as determined bywhat is known as the Zerewitinoff method) as an aid in building up apolyurethane molecular structure having desirable properties. Inpractice, the requirements of a chain extender can be quite complex andexacting, and unfortunately many of the conventional ones suffer fromvarious shortcomings in at least certain respects. One widely used chainextender is carcinogenic. To obviate this and other disadvantages therehas accordingly been a continuing search by those skilled in the art fornew chain extending agents.

The present invention is based on the discovery of certain newcompounds, believed to be noncarcinogenic, which are surprisingly usefulas chain extenders for polyurethanes. The new chemicals of the inventionare N,N'-bis( 1 l -dioxohydrothienyl)- diaminoalkanes having thefollowing formulas I or II:

Formula I X and Z may be the same or different and may be hydrogen, analkyl group having 1 to 5 carbon atoms or a halogen atom;

Y may be hydrogen, an alkyl group having 1 to 5 carbon atoms, or analkoxy group having 1 to 5 carbon I atoms;

R may be hydrogen, an alkyl group having 1 to 5 carwherein R R and R,may be the same or different and may be hydrogen or an alkyl grouphaving 1 to 5 carbon atoms.

The heterocyclic diaminoalkanes of this invention are useful as chainextenders for polyurethanes and specifically for high resiliency,flexible polyurethane foams which exhibit a unique combination ofphysical properties such as high tensile strength, high tear resistance,high elongation, high resilient properties and low compression set. Thechain extenders of the invention are also useful for making solidpolyurethane elastomers and thermoplastics, for example from castablepolyurethane prepolymers.

The novel compounds of this invention may be formed by a one-stepsynthesis starting with known thiophene l,l-dioxides and the appropriatediamines in a suitable solvent.

The N ,N '-bis( 1 l -di0xotetrahydro-3 thienyl)diaminoalkanes of FormulaI are fonned by reacting a 4,5-dihydrothiophene l,l-dioxide ill with theappropriate diaminoalkane IV according to the following scheme (whereinthe symbols have the meanings previously assigned):

The N,N'-bis[ 3-( l,1-dioxo-2,3-dihydrobenzo[b]- thienyl)]diaminoalkanesof Formula II may be formed by reacting a benz0[b]thiophene-l,l-dioxidewith the appropriate diaminoalkane Vl according to the following scheme(wherein the symbols are as defined above):

In general, 2 moles of the thiophene dioxide are reacted with 1 mole ofthe appropriate diaminoalkane. The reaction temperature is generallykept at 30l50C. and the reaction times will vary from 2 to 24 hoursdepending upon the thiophene dioxide and the diaminoalkane employed. Thereaction solvents used in this reaction are water, alcohol-watermixtures and alcohols. Examples of alcohols that may be employed includemethanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol andcyclohexanol.

Any of the 4,5-dihydrothiophene 1,1-dioxides having the followinggeneral formula (wherein X, Y, Z are as defined above) may be used asthe starting material III for making the N,N-bis(1,1-dioxotetrahydro-3-thienyl)diaminoalkanes I.

Similarly any of the benzo[b]thiophene 1,1-dioxides having the followinggeneral formula (wherein X and R are as defined above) may be used asthe starting material V for making the N,N'-bis[3-(l,l-dioxo-2,3-dihydrobenzo[b]thienyl)]diaminoalkanes ll.

7.. Particularly preferred chemicals of this subclass are N,- N'-[ 3-(1l-dioxo-2,3-dihydrobenzo[b]thienyl) ]-alpha, alpha'-diaminom-xylene andN,N'-bis[3-( l, l-dioxo- 2,3-dihydrobenzo[ b-lthienyl) l ,3-bis(aminomethyl cyclohexane.

To employ the present compounds as chain extending agents forpolyurethanes the compounds may simply besubstituted at least in partfor the conventional chain extending agents in any conventionalpolyurethane formulation of the kind ordinarily employing a chainextender. The proportions of thepresent chain extender employed may bethe same as in conventional practice and the chain-e xtending reactionmay-likewise be carried out under the same conditions as are usuallyemployed in conventionalpolyurethane chain extension. Polyurethanesystems of the socalled one-shot type, or of the prepolymer type, may beemployed, and the final product may be foam (either rigid or flexible)or a solid, whether elastomeric or otherwise, including thermoplasticpolyurethanes, polyurethane surface coatings, etc. As is well understoodby those skilled in the art, polyurethane forming systems conventionallyinvolve a combination of at least one long chain polyol (whether apolyester polyol, a polyether polyol or a polyhydrocarbon polyol) and atleast one organic polyytetramethylene) glycol, etc.] and higherpolyether polyols, such as triols [e.g. poly(oxypropylene triol)],including polyether polyols of higher functionality'than three [e.g.,poly( oxypropylene adducts of pentaerythritols) .and poly(oxypropyleneadducts of sorbitol)].

Mention may be made of such polyether polyols aspoly(oxypropylene)-poly(oxyethylene)glycol, poly(oxy{ propylene) adductsof trimethylol propane, poi1y( oxypropylene )-poly(oxyethylene )adductsof e trimethylolpropane, poly(oxyprop,ylene) adducts of" 1,2,6hexanetriol, poly(oxypropylene)-poly(o'xyethylene) adducts ofethylenediamine, poly(oxypropylene) adducts of ethanolamine, andpoly(oxypropylene) adducts of glycerine.-

The polyester types of polyols used in making polyurethanes are likewisewell known in the art and re-, 'quire no detaileddescription here. Itwill be'understood that they include chain extended polyesters made froma glycol ('e.g., ethylene and/or propylene glycol) and a saturateddicarboxylic acid (e.g., adipic acid). By way of non-limiting examplethere may be mentioned poly- (ethylene adipate) glycol, poly( propyleneadipate) glycol, poly(butylene adipate) glycol, poly(caprolactone)glycol, poly(ethylene adipate-phthalate) glycol, poly(- neopentylsebacate) glycol, etc. Small amounts of trialcohols such astrimethylolpropane or trimethylolethane may be included in the polyesterpreparation. Polyester polyols with functionalities of three or more[e.g., glycerides of l2-hydroxystearic acid] are also useful. Suitablepolyester polyols include those obtainable by reacting such polyols as1,4-butanediol, hydroquinone bis(2-hydroxyethyl) ether, ethylene glycol,diethylene glycol, triethylene glycol, propylene glycol, dipropyleneglycol, 2methyl-2-ethyl-1,3-propanedio], 2-ethyl- 1,3-hexanediol,1,5-pentanediol, thiodiglycol, 1,3- propanediol, 1,3-butanediol,2,3-butanediol, neopentyl glycol, "1,2-dimethyl-l,2cyclopentanediol,1,2-

cyclohexanediol, l,2dimethyll ,2-cyclohexanediol, glycerol, trimethylolpropane, trimethylol ethane, l,2,4'-butanetriol, 1,2,6-hexanetriol,pentaerythritol, dipentaerythritol, tripentaerythritol,anhydroaneaheptitol, mannitol, sorbitol, methylglucoside, and the like,with such dicarboxylic acids as adipic acid, succinic acid,glutaric'acid, azelaic acid, sebacic acid, malonic acid, maleic acid,fumaric acid, phthalic acid, isophthalic acid, terephthalic acid,tetrachlorophthalic acid, and chlorendic acid; the acid anhydrides andacid halides of these acids may also be used.

Among the polyhydrocarbyl polyols conventionally employed for makingpolyurethanes there may be mentioned by way of non-limiting example suchmaterials as poly( butadiene) polyols, poly( butadieneacrylonitrilepolyols and poly( butadiene-styrene) polyols.

The above polyols typically have a molecular weight or about 180 to8000.

Conventional polyisocyanates used in polyurethane manufacture include,as is well known, aliphatic polyisocyanates, whether open chain,cycloaliphatic or araliphatic. Examples of aliphatic polyisocyanatesconventionally employed are trimethylene diisocyanate, tetramethylenel,4f-diisocyanate, hexamethylene-l ,6- diisocyanate, l-methyl-2,4- and1-methyl-2,6- diisocyanatocyclohexane and mixtures thereof, pxylylenediisocyanate and m-xylylene diisocyanate (XDl) and mixtures thereof,4,4'-diisocyanatodicyclohexylmeth'ane, isophorone diisocyanate, 2,24-and 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Similarly, the aromatic polyisocyanates are suitable and include, by wayof non-limiting example, such bodies as 2,4-toluene diisocyanate and2,6-toluene diisocyanate and mixtures thereof (TDI, including crude andpolymeric forms), 4,4'-diphenylmethane diisocyanate (MDl, includingcrude and polymeric forms), pphenylene diisocyanate, 2,4,6-tolylenetriisocyanate,

4 ,4 4' -triphenylmethane triisocyan ate 2 ,2-bis(pisocyanato-phenyl)-propane, polymeric methylenebis(phenyl-4-isocyanate) (e.g. PAPl), naphthalenel,5-diisocyanate,3,3-dimethyl4,4'-biphenylene diisocyanate,3,3-dimethyoxy-4,4'-biphenylene diisocyanate,3,3'-diphenyl-4,4"-biphenylene diisocyanate, 4,4'-biphenylene vdiisocyanate, 3,3'-dichloro4,4'- biphenylene diisocyanate, and the like.Mixtures of two or more of such diisocyanates may also be used.Triisocyanates typically obtained by the reaction of 3 moles of anarylene diisocyanate with 1 mole of triol for example, the reactionproduct formed from 3 moles of tolylene diisocyanate and 1 mole ofhexanetriol or of trimethylol propane, may be employed.

In one important aspect, the invention is directed to an improvedflexible resilient polyurethane foam and method of making the same,employing the new chemicals described here-in as chain extenders. Thus,it is well based in part on the discovery that polyurethane foam havinga remarkable combination of desirable physical properties surprisinglyresults when the new N,N- bis( 1 ,1-dioxohydrothienyl)diaminoalkanes areemployed as bifunctional chain extenders. The foams of this inventionare characterized by high tensile strength, high tear resistance and lowcompression set. This unique combination of physical properties islargely determined by the unique chain extenders employed.

Formation of the preferred foamed products of this invention may beaccomplished in a one-shot system, by reacting the polyol with excesspolyfunctional isocyanate and the new chain extender of the invention inthe presence of water and cell modifying agents, eg silicone such astrimethyl end-blocked dimethyl polysiloxanes. The polyfunctionalisocyanate is typically present in amount of 5300%, say 40% by weight ofthe polyol. The binary chain extender of the invention is frequentlypresent in the one-shot foam formulation in amount of 0.5 to 15%,preferably 1 to by weight of the polyol. The water is employed in amountto react with the isocyanate to liberate sufficient gas (carbon dioxide)to produce a foam of the desired physical characteristics. From 0.6 to10%, say 4% water (by weight of polyol) will give good results.

The mixing of the constituents in the one-shot system is typicallyperformed at room temperature. The polyol, chain extender of theinvention, catalyst, water, flame retardant and other cell-modifyingagents (surface active agents) such as trimethyl end-blocked dimethylpolysiloxanes are first mixed and then the polyisocyanate is added withvigorous stirring. The gas forming reaction, the chain extension and thecross linking reactions start simultaneously when the polyisocyanate isadded.

Some examples of useful catalysts are N- methylmorpholine,N-ethyl-morpholine, triethyl amine, triethylene diamine (Dabco),N,N-bis(2- The resulting one-shot foams of the invention surprisinglyare characterized by a unique combination of physical properties such ashigh tensile strength, high tear resistance, high elongation, goodresilience prop erties and low compression set. These flexible foamsfind utility as automobile and furniture cushioning materials, pillows,mattresses and carpet underlays.

Another important form of the invention is concerned with solidpolyurethanes, particularly those made by the so-called prepolymertechnique wherein the polyol is prereacted with an excess of thepolyisocy- EXAMPLE 1 3-thienyl)-1,Zdiaminoethane, obtained was a viscousanate, and thereafter the prepolymer is chain-extended or cured, usingthe bifunctional chain extending agent of the invention. Using liquidprepolymers cast elasto meric (or thermoplastic) articles and coatingshaving highly useful properties may be made in this way.

The following examples demonstrate the invention.

liquid that became a solid, mp. 60 C. IR spectrum showed absorptions at3300 cm (NH), at 1300 cm and 1140 cm"(SO Analysis for C H N O S(percent): Calcd. for C, 40.52; H, 6.80; N, 9.45; S, 21.63 Found: C,40.52; H, 6.85; N,9.10; 20.96.

EXAMPLE 2 EXAMPLE 3 Example 1 was repeated using the dioxide of Examplel and substituting 1,2-diaminopropane for 1,2- diaminoethane. Theresultant product, N,N-bis(l,1-dioxotetrahydro-B-thienyl)'1,2-diaminopropane obtained was a viscousliquid. The infrared spectrum showed absorptions at 3280 cm (NH), at1300 cm and 1 cm ($0 The NMR spectrum showed the bands with relativeareas in agreement with the structure.

Analysis for C H N O S (percent): Cald for C, 42.56; H, 7.14; N, 9.03;S, 20.65. Found: C, 42.27; H, 7.26; N, 9.03; S, 19.98.

EXAMPLE 4 Example 1 was repeated using the thiophene dioxide of Example1, but substituting l,4-diaminobutane for 1,2-diaminoethane. Theproduct, N,N-bis(l,ldioxotetrahydro-3-thienyl l ,4-diaminobutaneobtained was a viscous liquid. The infrared spectrum showed absorptionsat 3300 cm (NH), at 1310 cm and 1150 cm (S0 Analysis for C H N O S(percent): Cald for C, 44.42; H, 7.45; N, 8.70; S, 19.76. Found: C,44.59; H, 7.59; N, 8.61; S, 19.27.

EXAMPLE 5 Example 1 was repeated using the thiophene dioxide of Example1 and substituting 1,2-diamino-2- methylpropane for 1,2-diaminoethane.The resultant product, N ,N'-bis( 1,1-dioxotetrahydro-3-thienyl)-l ,2-diamino-Z-methylpropane was obtained as a viscous liquid. The infraredspectrum and the NMR spectrum are in agreement with the structure.

11 Analysis for C H N O S (percent): Calcd for C, 44.42; H, 7.45; N,8.70; S, 19.76. Found: C, 44.45; H, 7.66; N, 9.25; S, 19.27.

EXAMPLE 6 Example 1 was repeated using the thiophene dioxide of Example1 and substituting 1,6-diaminohexane for 1,2-diaminoethane. Theresultant product, N,N- bis( 1,1-dioxotetrahydro-3-thieny1)-1,6-

diaminohexane, obtained was a white solid, m.p.

102-112C. (from ethanol).

The infrared spectrum showed absorptions at 3285 cm (NH), at 1310 cm'and 1150 cm (S Analysis for C H N O S (percent): Calcd for C, 47.70; H,8.00; N, 7.94; S, 18.17. Found: C, 47.77; H, 7.92; N, 7.91; S, 18.12.

EXAMPLE 7 EXAMPLE 8 Example 1 was repeated using the thiophene dioxideof Example 1 and substituting 1,10-diaminodecane for 1,2-diaminoethane.The resultant product, N,N- bis( 1 ,1-dioxotetrahydro-3-thieny1)-l ,10-diaminodecane obtained was a white solid, m.p. ll17C. The infraredspectrum showed absorptions at 3300 cm (NH), at 1310 cm" and 1120 cm 2)Analysis for C H N O S (percent): Calcd for C, 52.90; H, 8.80; N, 6.86;S, 15.69. Found: C, 52.92; H, 9.17; N, 6.70; S, 15.47.

EXAMPLE 9 Example 1 was repeated using the thiophene dioxide of Example1 and substituting 1,6-diamino-2,2,4- trimethylhexane for1,2-diaminoethane. The resultant product, N,N '-bis( 1,1-dioxotetrahydro-3-thienyl)-1,6- diamino-2,2,4-trimethylhexaneobtained was viscous liquid. The infrared spectrum showed absorptions at3290 cm* (NH), at 1310 cm and 1130 cm (SO Analysis for C, H ,N O S(percent): Calcd for C, 51.75; H, 8.69; N, 7.10; S, 16.25. Found: C,51.77; H, 8.94; N, 7.18; S, 15.88.

EXAMPLE 10 Example 1 was repeated using the thiophene dioxide of Example1 but substituting alpha,alpha-diamino-mxylene for 1,2-diaminoethane.The resultant product, N,N'-bis( 1 1 -dioxotetrahydro-3-thienyl)-alpha,alpha'- diamino-m-xylene obtained was a viscous liquid. Theinfrared spectrum showed absorptions at 3350 cm" (NH) at 1300 cm and1125 cm(SO at 780 cm and 705 cm (aromatic).

Analysis for C H N O S (percent): Calcd for C, 51.59; H, 6.50; N, 7.52;S, 17.21. Found: C, 52.13; H, 6.71; N, 7.86; S, 16.69.

EXAMPLE 1 1 Example 1 was repeated using the diaminoalkane of Example 1and substituting 2-chloro-4,S-dihydrothiophene 1, l-dioxide for4,5-dihydrothiophene 1,1- dioxide. The resultant product, N,N-bis(1,1-dioxo-2- chlorotetrahydro-3-thienyl)-1,Z-diaminoethane obtained wasa white solid, m.p. l42-l50C (dec.) The infrared spectrum showedabsorptions at 3300 cm (NH), at 1300 cm and 1125 cm (S0 Analysis for C HCl N O S (percent): Calcd for C, 32.88; H, 4.97; CI, 19.41; N, 7.67; S,17.55. Found; C, 32.59; H, 4.98; Cl, 19.43; N, 7.47; S, 17.25.

EXAMPLE 12 Example 1 was repeated using the thiophene dioxide of Example1 and substituting 4,4-methylenebis(aminocyclohexane) for1,2-diaminoethane. The resultant product N,N -bis( 1 1-dioxotetrahydro-3- thienyl)-4,4'-methylene-bis(aminocyclohexane)obtained was a white solid, m.p. 1902l0C (dec.). The infrared spectrumshowed absorptions at 3270 cm" (NH), at 1310 cm and 1120 cm (S0 Analysisfor C H N O,S (percent):

Analysis for C ,H N O S (percent): Calcd for C, 56.47; H, 8.50; N, 6.27;S, 14.33. Found: C, 56.97; H, 8.51; N, 6.36; S, 13.78.

EXAMPLE 13 Example 1 was repeated using the thiophene dioxide of Example1 and substituting l,3-bis(aminomethyl)cyclohexane for1,2-diaminoethane. The resultant product, N,N'-bis( l,1-dioxotetrahydro-3-thienyl)-1,3-bis- (aminomethyl)-cyclohexane.obtained was a viscous liquid. The infrared spectrum showed absorptionsat 3300 cm" (NH), at 1310 cmand 1110 cm" (S0 Analysis for C ,,-H N O S(percent): Calcd for C, 50.76; H, 7.98; N, 7.39; S, 16.93. Found: C,50.83; H, 8.06; N, 7.34; S, 16.50.

EXAMPLE 14 This example illustrated the preparation of typical N,N'-bis[3-(1,1-dioxo-2,3-dihydrobenzo[b]thienyl)- ]diaminoalkane II of thisinvention, N,N'-bis[3-(l,ldioxo-2,3-dihydrobenzo[b]thienyl ]-1 ,2-diaminoethane, following the procedure of Example 1 and using1,2-diaminoethane as the diaminoalkane and substitutingbenzo[b]thiophene 1,1-dioxide for 4,5-dihydrothiophene 1,1-dioxide. Thereaction mixture was heated at reflux (C) for 20 hours and allowed tocool at room temperature. The solid product collected by filtration wasdried in air, m.p. 189190C. The infrared spectrum of this product, N,-N'-bis[3-( 1,1-dioxo-2,3-dihydrobenzo[b]thienyl)]- 1,2- diaminoethane,showed absorptions at 3300 cm (NH), at 1300 cm and 1130 cm (SO at 790 cmand 760 cm (aromatic).

Analysis for C H N O S (percent): Calcd for C, 55.08; H, 5.14; N, 7.14;S, 16.34. Found: C, 55.14; H, 5.25; N, 7.00; S, 16.09.

A second isomer was isolated from the above reaction when the filtrateof the first product was cooled in ice-water. This isomer, m.p. 11 1-112C had a similar infrared spectrum to the first product. However, thetwo spectra were similar, but not superimposable. The

spectrum of the second product also showed absorptions at 3300 cm (NH),at 1300 cm and 1130 cm (S at 790 cm and 760 cm (aromatic).

The NMR spectra of two isomers are vertually identical and in agreementwith the structure N,N-bis[3-1,l-dioxo-2,3-dihydrobenzo[b]thienyl)]-1,2- diaminoethane.

Analysis for second isomer C H N Ofi (percent): Calcd for C, 55.08; H,5.14; N, 7.14; S, 1634. Found: C, 54.89; H, 5.27; N, 7.01; S, 16.07.

EXAMPLE Example 14 are repeated using the thiophene dioxide of Example14 but substituting 1,2-diaminopropane for 1,2-diaminoethane. Theresultant product, N,N-bis[3- (1, l-dioxo-2,3-dihydrobenzo[b]thienyl) l,2- diaminopropane isolated was a white solid, mp. 163167C. (dec.) Theinfrared spectrum showed absorptions at 3300 cm" (NH), at 1300 cm and1125 cm (S0 at 790 cm and 760 cm (aromatic).

Analysis for C H N O S (percent): Calcd for C, 56.13; H, 5.45; N, 6.89;S, 15.77. Found: C, 56.23; H, 5.58; N, 6.94; S, 15.70.

EXAMPLE 16 EXAMPLE 17 Example 14 was repeated using thiophene dioxide ofExample 14 but substitutiing a,a-diamino-m-xylene for 1,2-diaminoethane.The resultant product, N,N'-[3- l, l-dioxo-2,3-dihydrobenzo[b]thienyl]-alpha,alpha'-diamino-m-xylene obtained was a viscous liquid thatbecame solid (glass).

Analysis for C H N O S (percent): Calcd C, 61.51; H, 5.16; N, 5.97; S,13.68. Found: C, 61.99; H, 5.28; N, 5.88; S, 13.32.

EXAMPLE 18 This example illustrates that the N,N-bis( 1,1-dioxotetrahydro-3-thienyl)diaminoalkanes of this invention can also beprepared from 2,5-dihydrothiophene 1,1-dioxides and the appropriatediaminoalkanes in the presence of a base as catalyst.

To a 500 ml round-bottom flask equipped with condenser, thermometer anda stirrer were introduced 1 18 g. (1.0 mole) of 2,5-dihydrothiophene1,1-dioxide, 200 m1; of 70% by weight aqueous ethanol and 37 g (0.5mole) of 1,2-diaminopropane and 10 ml. of a 0.1 N sodium hydroxidesolution. The reaction mixture was heated at 85C for 20 hours. Thesolvent was then removed under a reduced pressure. The product, N,N-bis( 1, l-dioxotetrahydro-3-thienyl)- l ,2- diaminopropane was obtainedas a viscous liquid. The infrared spectrum of this product wassuperimposable with that of Example 3. This product also evaluated in 14high resiliency, flexible polyurethane foam (see Example 19).

As indicated above, the novel compounds this invention find use as chainextenders in the one-shot system of solid foamed polyurethanes. In thissystem, the mixing of the constituents is typically performed at roomtemperatures. The polyol (polyester polyol, polyether polyol orpolyhydrocarbon polyol), chain extender, catalyst, water, flameretardant and other cellmodifying agents (surface active agents), arefirst mixed and then the polyisocyanate is added with vigorous stirring.The gas forming reaction, the chain extension and the cross linkingreactions start simultaneously when the polyisocyanate is added.

The formation of foamed products is accomplished in the one-shot systemby reacting the polyol with a slight excess typically about 5 to 10equivalent weight percent excess, of polyfunctional isocyanate in thepresence of water and cell modifying agents, e.g. silicones such astrimethyl end-blocked dimethyl polysiloxanes. The polyfunctionalisocyanate is typically present in amount of 5300%, say 40%, by weightof the polyol. The water should be present in amount to react with theisocyanate to liberate sufficient gas (carbon dioxide) to produce a foamof the desired physical characteristics. From 0.5 to 10%, say 3% water(by weight of polyol) will give good results. Some examples of usefulcatalysts are N-methylmorpholine, N-ethylmorpholine, triethyl amine.triethylene diamine (Dabco, trademark),N,N'-bis(2-hydroxypropyl)-2-methyl piperazine, dimethyl ethanol amine,tertiary amino alcohols, tetiary ester amines and the like. For furtherdetails on the formulation of polyether-polyol based one shot foamformulations reference may be had to copending application Ser. No.336,842 of Mao and Bakker, filed Feb. 28, 1973, and now US. Pat. No.3,821,132, the disclosure of which is hereby incorporated herein byreference. An example of this form of the invention is as follows:

EXAMPLE 19 This example demonstrates the use of several novel compoundsof this invention as binary chain extenders in the preparation of foamedpolyurethane structures using an otherwise conventional high resiliencyfoam formulation. For comparison purposes, the most widely used chainextender, 4,4-methylene-bis(ochloroaniline), which is commonlydesignated by the code letters MOCA was also used. The formulations andresults are tabulated in Table 1.

It should be noted that the polyurethane foamed structures A to F madewith the novel compounds of this invention exhibit a unique combinationof physical properties such as high tensile strength, high tearresistance, high elongation, high resilient properties and lowcompression set.

In Table I the formulations are expressed in parts by weight. The polyolis polypropyleneglycoltriol, molecular weight about 4700 made frompropylene glycol (initiated with a tri-functional initiator, such asglycerol) and end-capped with, for example, 30% ethylene oxide (VoranolCP-4701; trademark). As indicated in the table the chain extenders arethe compound of Example 1 (formulation A), Example 3 (formulationB,C,D), Example 5 (formulation E), and Example 18 (formulation F), aswell as the conventional MOCA (formulation G). T-23P indicates a fireretardant, tris(2,3-

' 1S dibromopropyl)phosphate (Firemaster T23P; trademark). The firstthree catalysts listed are amine types, as follows: Dabco is1,4-diazobicyclo [2.2.2] octane;

vated temperatures ranging from 70 to about 1 10C as shown in Table II.The resultant reaction mixture'is then poured into a mold, cured forabout one hour at determined excess of a diisocyanate with a polyester,polyether or polyhydrocarbon polyol such as PTMG (polytetramethyleneglycol)diol and the resulting prepolymer is mixed with the binary chainextender at ele- NEM is N-ethyl morpholine; A-l is bis(2- about 120C andconditioned in air at 25C and 50% dimethylaminoethyl) ether (NIAX A-l;trademark). 5 relative humidity for 14 days before testing. The nextcatalyst listed, T-l2 (trademark), is an organ- This procedure isemployed to prepare cured ply otin catalyst, dibutyl tin dilaurate. Thesiloxane ls dlmeurethanes H, I, L K L, M and N shown in Table [L In l py siloxane p trademark) m toluene stocks H and I the prepolymer is aliquid urethane reacdllsPcyanate 23- zil'lsomefi by tion product ofhydroxy terminated polyester (e.g. eth- PAPI polynleflc 4,4 f' yleneglycol adipate) with a slight excess of a polyisocydlphenyldllsocyanate-The f of D q PAP! anate (e.g. TDI), having an isocyanate content of ap-90/10 "1 all cases- The f l y expressed P l-" proximately 3%, an amineequivalent of about 1300, a P c9919 foot: the tenslle m p Pe Squaremolecular weight of about 2500, specific gravity 1.2, The unfts arePounds P h elonviscosity 500 centpoi'ses at 158F, 1,500 centipoises atgation 15 Elven P fl- T Set 15 l"- 1 212F. The prepolymer used in stocksJ and K is a liq- Pression expresse P f ILD mdlc'fnes the uid urethanereaction product of a polyether glycol dentatio n load deflectlon (that1s, the load necessary to (e.g. polytetramethylene ether l l i h a li hproduce O 65% fl eXPKiSSed P d cess of a polyisocyanate (e.g. TDI)having an isocyaper Square nc ese g is the ratio of the natecontent ofapproximately 3%, an amine equivalent ILD to the 25% lLD. All theproperties were deterof about 1355, a viscosity of about 8 poises at158F mined accdl'ding to ASTM D'2406'68 p and a specific gravity of1.04. The prepolymer used in in each formulation in Table l the polyol,chain 615- st ck L, M and N was a polyether (polytetramethylene tender,catalyst, water, flame retardant and cell modlth l l) b d li id polymeri h a li h excess fyingagent (siloxane) are first mixed at roomtemperaof a polyisocyanate (e.g. TDI) having an isocyanate ture and thenthe polyisocyanate is added (also at room 25 (NCO) content of 6.05 to6.55%, an amine equivalent temperature) with vigorous stirring; theliquid mixture of about 665, and a viscosity of 6 poises at 158F. andquickly'foa'm's up and solidifies, forming a resilient a specificgravity 1.07. In stock H the chain extender p l urethanes foam, is thecompound of Example 1; stocks I and J use the TABLE 1 One-ShotPolyurethane Foam MATE- SA 13 c D E F o RIAL 1 Polyol v 100 100 100 100100 100 Ex. 1 5.0 Ex. 3 5.0 3.0 1.0 Ex,.5 5.0 Ex; 18 5.0 MOCA 5.0 Water3.5 3.5 3.5 3.5 3.5 3.5 3.5 T-23 P 3.0 3.0 3.0 3.0 3.0 3.0 3.0Catalysts: I Dabco 0.6 0.6 0.6 0.5 0.5 0.6 0.6 NEM 0.75 0.75 0.75 0.30.3 0.75 0.75 Al 0.15 0.15 0.15 0.15 0.15 0.15 0.15 T-l2 0.0075 0.00750.0075 0.0075 0.0075 Siloxane 1.0 1.0 1.0 1.0 1.0 1.0 1.0 TDI i 39.139.4 39.3 39.1 39.3 39.4 39.9 PAPl 6.8 6.7 6.6 6.4 6.6 6.7 6.9Properties Density 1 2.00 2.35 2.19 2.29 2.06 2.32 2.41 Tensile 26.020.8 18.07 17.1 1, 22.46 22.86 22.03 Tear 2.57 2.32 2.05 2.02 1.99 2.341.87 Elongation 182 184 193 195 183 139 s t 50% 8.0 17.4 14.9 17.4 10.39.4 75% 9.2 11.8 11.4 13.7 11.7 11.4

'ILD

25% 21.5 21.7 15.6 19.0 14.5 22.2 23.2 65% 65.5 66.8 51.9 59.8 51.8 66.875.2 Sag 3.04 3.08 3.33 3.15 3.57 3.01 3.26

EXAMPLE 20 1 chain extender of Example 2; stock K has the chain extenderof Example 3; stock L has the chain extender of As indicated above, thenovel N,N'-bis( 1 ,1- Example 16; stock M has the chain extender ofExamdioxotetrahydro-3-thienyl)diaminoalkanes also find 60 ple 13, andstock N the chain extender of Example 17. use as binary chain extendersfor castable solid poly- The amountsof prepolymer and chain extender areas urethanes made from polyester or polyether or shown in Table Il,expressed in parts by weight. In polyhydrocarbon-TDl-based prepolymers.In this sys- Table II the tensile strength is expressed in pounds pertem the prepolymer is first prepared by reacting a pre- 65 square inch.The tensile and elongation (percent elongation at break) were determinedby following method ASTM D41 2-68 and Scott Model L Tester instructions.A jaw separation rate of 20 in./min. and a sample thickness of 0.10 inchwere used. The tear (poundsper lincar inch) was obtained by followingprocedure of ASTM 624-54 but using a sample measuring 3 X 1 inches whichwas died out from a sheet of stock 0.10 inch thick with a 2 inch slitextending lengthwise from one end. The two legs were put in the jaws ofa Scott Tester Model L and elongated until torn apart. The forcerequired to accomplish this was recorded. The hardness (Shore A) wasdetermined according to ASTM D2240-68. The modulus (at 100% elongation,expressed in pounds per square inch) was determined from autographicstress-strain measurements. A 0.10 inch thick sample is died ouot into aring, 3 cm. inner diameter, 3.5 cm. outer diameter, placed around pulluprotating at 200 rpm and elongated at a rate of inches per minute. Thestress values were determined at 100% elongation.

TABLE 11 Solid Polyurethanes H l J K L We claim:

1. A polyurethane which is a reaction product of a long chain polyolselected from the group consisting of polyesters. polyethers andpolyhydrocarbons with a chain extender and with a polyisocyanate, thesaid chain extender being a compound which is an N,N'- where R and R andR, are the same or different and bis( 1,1-dioxohydrothienyl)diaminoalkane having one of the following formulas l or 11:

are hydrogen or an alkyl group having 1 to 5 carbon atoms.

- u-n-a wherein 2. A polyurethane as in claim 1 in which the said chainextender is an N,N-bis( l,1-dioxohydrothienyl)- diaminoalkane having thesaid formula 1, wherein X, Y and Z are hydrogen, and R is an alkylenegroup having 2 to 12 carbon atoms.

3. A polyurethane as in claim 2 in which water is a additional reactantand the polyurethane is a foam.

4. A polyurethane as in claim 1 in which the said chain extender is anN,N-bis( l,l-dioxohydrothienyl)- diaminoalkane having the said formula1, wherein X is hydrogen or halogen, Y and Z are the same or differentand are hydrogen or an alkyl group having 1 to 5 car- "19 20 bon atomsand R is an alkylene group having 2 to 12 7. A polyurethane as in claim1 in which the said carbon atoms. a cycloalkylene group having 4 to 6carh i extender i .N N'-bi l l di t t h d -3- bon atoms. thienyl-)- l.Z-diaminoethane.

8. A polyurethane as in claim I in which the said chain extender isN,N-bis( l.l-dioxotetrahydro-3- thienyl)-l.Z-diaminopropane.

9. A polyurethane as in claim 1 in which the said chain extender isN,N'-bis( Ll-dioxotetrahydro-3- thienyH-l .3-diaminopropane.

l0 10. A polyurethane as in claim 1 in which the said chain extender isN,N-bis( l.l-dioxotetrahydro-3- thienyl l .Z-diamino-Z-methylpropane.

11. A polyurethane as in claim 1 in which the said chain extender isN,N-bis( 1,1-dioxotetrahydro-3- or is thienyl)- l,3-bis(aminomethyl)cyclohexane.

12. The polyurethane as in claim 1 in which the said chain extender I vis N.N'-[3-( l,l-dioxo-2,3- dihydrobenzol b ]thienyl ]-alpha,alpha'-diamino-mxylene.

- 13. A polyurethane as in claim 1 in which the said chain extender isN,N-bis[3-( l,l-dioxo-2,3- dihydrobenzol blthienyl 1 ,3-bis( aminomethyl)cy- CH clohexane.

2 14. A polyurethane foam made from the reaction products of apolyalkylene polyether polyol having a hydroxylic functionality of atleast two. an organic- 5. A polyurethane as in claim 1 in which the saidpolyisocyanate and a chain extender in the present of chain extender isan N,N-bis( l. l-dioxohydrothienyl)- a blowing agent. the said chainextender being an N.N"- diaminoalkane having the said formula ll,wherein X is bis( l.l-diox0hydrothienyl)diaminoalkane having onehydrogen. R is hydrogen, an alkyl group having 1 to 5 of the followingformulas l or ll:

H H Y IL Y II AMAIU z 8 x x s z H H g i h- R R R1 S x x g 0 2 n carbonatoms or halogen, and R is an alkylene group h e 1 having 2 to 12 carbonatoms. i i X and Z are the same or different and are hydrogen.

6. A polyurethane as in claim 1 in which'the said 7 an alkyl grouphaving 1 to 5 carbon atoms or halochain extender is an N.N'-bis(l,l-dioxohydrothienyl)- gen, 7 diaminoalkane having the said formula ll,wherein X is Y is hydrogen, an alkyl group having 1 to 5 carbon hydrogenor halogen, R is hydrogen, a lower alkyl atoms, or an alkoxy grouphaving 1 to 5 carbon group having 1 to 5 carbon atoms or halogen, and Ris atoms; V

' .R, is hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkoxygroup having l to 5 carbon atoms CH or halogen;' I I CH or R is analkylene group having 1 to 16 carbon atoms, a cycloalkylene grouphaving4 to 6 carbon atoms,

where R R and R are the same or different and are hydrogen or an alkylgroup having 1 to 5 carbon atoms.

15. Polyurethane foam as in claim 14 in which the said chain extender isan N,N'-bis( l,l-dioxohydrothienyl)diaminoalkane having the said formulaI. wherein X, Y and Z are hydrogen, and R is an alkylene group having 2to 12 carbon atoms.

16. Polyurethane foam as in claim 14 in which the said chain extender isan N,N'-bis( 1,1-dioxohydrothienyl)diaminoalkane having the said formulaI, wherein X is hydrogen or halogen, Y and Z are the same or differentand are hydrogen or an alkyl group having I to 5 carbon atoms and R isan alkylene group having 2 to 12 carbon atoms, a cycloalkylene grouphaving 4 to 6 carbon atoms.

17. Polyurethane foam as in claim 14 in which the said chain extender isan N,N-bis( 1,1-dioxohydrothienyl)diaminoalkane having the said formulaII, wherein X is hydrogen, R is hydrogen, an alkyl group having 1 to 5carbon atoms or halogen, and R is an alkylene group having 2 to 12carbon atoms.

18. Polyurethane foam as in claim 14 in which the said chain extender isan N,N'-bis(l,l-dioxohydrothienyl)diaminoalkane having the said formula[1, wherein X is hydrogen or halogen, R, is hydrogen, a lower alkylgroup having 1 to 5 carbon atoms or halogen, and R is CH or S CH l9.Polyurethane foam as in claim 14 in which the said chain extender isN,N-bis( l,l-dioxotetrahydro-3- thienyl )l ,Z-diaminoethane.

20. Polyurethane foam as in claim 14 in which the said chain extender isN,N-bis( 1,1-dioxotetrahydro-3- thienyl l ,Z-diaminopropane.

21. Polyurethane foam as in claim 14 in which the said chain extender isN,N-bis( 1,1-dioxotetrahydro-3- thienyl)-l ,3-diaminopropane.

22. Polyurethane foam as in claim 14 in which the said chain extender isN,N'-bis( l,l-dioxotetrahydro-3- thienyl )-l .2-diamino-2-methylpropane.

23. Polyurethane foam as in claim 14 in which the said chain extender isN,N'-bis( l,l-dioxotetrahydro-3- thienyl l,3-bis(aminomethyl)cyclohexan'e.

24. Polyurethane foam as in claim 14 in which the said chain extender isN,N-[3-(l,l-dioxo-2,3- dihydrobenzolbhhienyl) ]-alpha,alpha'-diamino-mxylene.

25. Polyurethane foam as in claim 14 in which the said chain extender isN,N'-bis[3-( l,l-dioxo-2,3-dihydrobenzo[b]thienyl)1-1,3-bis(aminomethyl)cyclohexane.

1. A POLYURETHANE WHICH IS A REACTION PRODUCT OF A LONG CHAIN POLYOLSELECTED FROM THE GROUP CONSISTING OF POLYESTERS, POLYESTHERS ANDPOLYHDROCARBONS WITH A CHAIN EXTENDER AND WITH A POLYISOCYANATE, THESAID CHAIN EXTENDER BEING A COMPOUND WHICH IS AN N, N'' -BIS(1,1-DIOXOHYDROTHIENYL DIAMONOALKANE HAVING ONE OF THE FOLLOWING FORMULAS 1OR 11:.
 2. A polyurethane as in claim 1 in which the said chain extenderis an N,N''-bis(1,1-dioxohydrothienyl)diaminoalkane having the saidformula I, wherein X, Y and Z are hydrogen, and R is an alkylene grouphaving 2 to 12 carbon atoms.
 3. A polyurethane as in claim 2 in whichwater is an additional reactant and the polyurethane is a foam.
 4. Apolyurethane as in claim 1 in which the said chain extender is anN,N''-bis(1,1-dioxohydrothienyl)diaminoalkane having the said formula I,wherein X is hydrogen or halogen, Y and Z are the same or different andare hydrogen or an alkyl group having 1 to 5 carbon atoms and R is analkylene group having 2 to 12 carbon atoms, a cycloalkylene group having4 to 6 carbon atoms,
 5. A polyurethane as in claim 1 in which the saidchain extender is an N,N''-bis(1,1-dioxohydrothienyl)diaminoalkanehaving the said formula II, wherein X iS hydrogen, R1 is hydrogen, analkyl group having 1 to 5 carbon atoms or halogen, and R is an alkylenegroup having 2 to 12 carbon atoms.
 6. A polyurethane as in claim 1 inwhich the said chain extender is anN,N''-bis(1,1-dioxohydrothienyl)diaminoalkane having the said formulaII, wherein X is hydrogen or halogen, R1 is hydrogen, a lower alkylgroup having 1 to 5 carbon atoms or halogen, and R is
 7. A polyurethaneas in claim 1 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diaminoethane.
 8. Apolyurethane as in claim 1 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diaminopropane.
 9. Apolyurethane as in claim 1 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,3-diaminopropane.
 10. Apolyurethane as in claim 1 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diamino-2-methylpropane.11. A polyurethane as in claim 1 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,3-bis(aminomethyl)cyclohexane.12. The polyurethane as in claim 1 in which the said chain extender isN,N''-(3-(1,1-dioxo-2,3-dihydrobenzo(b)thienyl))-alpha,alpha''-diamino-m-xylene.
 13. A polyurethane as in claim 1 in which the said chainextender is N,N''-bis(3-(1,1-dioxo-2,3-dihydrobenzo(b)thienyl))-1,3-bis(aminomethyl)cyclohexane.
 14. A polyurethane foam made from thereaction products of a polyalkylene polyether polyol having a hydroxylicfunctionality of at least two, an organic polyisocyanate and a chainextender in the present of a blowing agent, the said chain extenderbeing an N,N''-bis(1,1-dioxohydrothienyl)diaminoalkane having one of thefollowing formulas I or II:
 15. Polyurethane foam as in claim 14 inwhich the said chain extender is anN,N''-bis(1,1-dioxohydrothienyl)diaminoalkane having the said formula I,wherein X, Y and Z are hydrogen, and R is an alkylene group having 2 to12 carbon atoms.
 16. Polyurethane foam as in claim 14 in which the saidchain extender is an N,N''-bis(1,1-dioxohydrothienyl)diaminoalkanehaving the said formula I, wherein X is hydrogen or halogen, Y and Z arethe same or different and are hydrogen or an alkyl group having 1 to 5carbon atoms and R is an alkylene group having 2 to 12 carbon atoms, acycloalkylene group having 4 to 6 carbon atoms.
 17. Polyurethane foam asin claim 14 in which the said chain extender is anN,N''-bis(1,1-dioxohydrothienyl)diaminoalkane having the said formulaII, wherein X is hydrogen, R1 is hydrogen, an alkyl group having 1 to 5carbon atoms or halogen, and R is an alkylene group having 2 to 12carbon atoms.
 18. Polyurethane foam as in claim 14 in which the saidchain extender is an N,N''-bis(1,1-dioxohydrothienyl)diaminoalkanehaving the said formula II, wherein X is hydrogen or halogen, R1 ishydrogen, a lower alkyl group having 1 to 5 carbon atoms or halogen, andR is
 19. Polyurethane foam as in claim 14 in which the said chainextender is N,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diaminoethane.20. Polyurethane foam as in claim 14 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diaminopropane. 21.Polyurethane foam as in claim 14 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,3-diaminopropane. 22.Polyurethane foam as in claim 14 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,2-diamino-2-methylpropane.23. Polyurethane foam as in claim 14 in which the said chain extender isN,N''-bis(1,1-dioxotetrahydro-3-thienyl)-1,3-bis(aminomethyl)cyclohexane.24. Polyurethane foam as in claim 14 in which the said chain extender isN,N''-(3-(1,1-dioxo-2,3-dihydrobenzo(b)thienyl))-alpha,alpha''-diamino-m-xylene.
 25. Polyurethane foam as in claim 14 in which the said chainextender is N,N''-bis(3-(1,1-dioxo-2,3-dihydrobenzo(b)thienyl))-1,3-bis(aminomethyl)cyclohexane.